Isothiazole type azo dyes containing imidazo type couplers

ABSTRACT

Disclosed are novel azo dyes containing an isothiazole azo moiety which may be substituted, and a heterocyclic coupler which also may be substituted. The dyes produce yellow shades on, for example, hydrophobic textile fiber including polyesters, polyamides, and cellulose esters and have excellent fastness properties including lightfastness, washfastness and resistance to sublimation, and dye at unusually low energy levels. The dyes have the general formulae: ##STR1## wherein the various substituents, R 1  and R 2  are each selected from hydrogen and a wide variety of groups such as lower alkyl, --CN, halogen, and the like, R 3  and R 4  are each selected from hydrogen, lower alkyl, benzyl and phenyl, and Z represents the atoms necessary to complete a five or six membered ring.

This is a division of Application Ser. No. 128,209, filed Mar. 7, 1980,now U.S. Pat. No. 4,354,970 issued Oct. 19, 1982.

This invention relates to novel azo dyes containing an azo isothiazolemoiety which may be substituted, and a heterocyclic coupler which alsomay be substituted. The dyes produce yellow shades on hydrophobictextile fiber including polyesters, polyamides, and cellulose esters andshow unexpected improvements in one or more of such properties asfastness to light, wash, ozone, gas such as oxides of nitrogen,perspiration, crock, sublimation, dyeability at unusually low energylevels to deep shades and exhibit excellent build, pH stability, bloomresistance, leveling, migration, dye bath exhaustion, dye transfer, andthe like, over such prior art as disclosed in U.S. Pat. Nos. 3,928,311;3,143,540; and 3,804,823.

The dyes of this invention have the following general formulae: ##STR2##wherein R¹ and R² are each selected from cyano, bromo, hydrogen, chloro,formyl, lower alkoxycarbonyl, lower alkyl, lower alkylsulfonyl,thiocyanto, carbamoyl, lower alkylcarbamoyl, and lower alkanoyl; R³ andR⁴ are each selected from hydrogen, lower alkyl, benzyl and phenyl; andZ represents the atoms necessary to complete a five or six memberedring.

The carbocyclic aryl groups represented by Ar can be unsubstituted orsubstituted with lower alkyl, lower alkoxy, halogen, hydroxy, loweralkylamino, nitro, cyano and the like. Specific examples of such phenylgroups include but are not limited to phenyl, p-tolyl, m-ethylphenyl,p-anisyl, p-chlorophenyl, o-bromo-p-tolyl, o,p-dichlorophenyl,p-cyanophenyl.

The carbon atoms of the groups represented by Z can be substituted ordisubstituted. Typical examples of the ring atoms that Z can representare ##STR3## The carbon atoms of the divalent groups represented by Zcan be substituted with various substituents including a fusedcarbocyclic ring which may also be substituted. Examples of suchsubstituents are hydrogen, oxygen, lower alkyl, lower alkoxy, halogen,lower alkylsulfonyl, thiocyanato, alkylthio, etc. As used herein todescribe a substituent containing an alkyl or alkylene moiety, the word"lower" designates a carbon content of one to four carbon atoms. Typicalof the groups represented by the divalent chain Z include the followinggroups ##STR4## wherein R⁵ represents a group selected from hydrogen,lower alkyl, lower alkoxy, halogen, and preferably, not more than twosubstituents.

A preferred group of the coupler components of the novel compounds ofthe invention have the formula ##STR5## wherein Ar represents phenyl orphenyl substituted with lower alkyl; and R⁵ represents hydrogen andlower alkyl. Especially preferred are the coupler components conformingto the above structure to which R⁵ is attached.

The monoazo compounds of the invention are prepared by diazotizing anamine having the formula: ##STR6## and coupling the resulting diazoniumsalt with a compound having the formula ##STR7## wherein Ar and Z aredefined above. The amines of Formula III and the coupling proceduresthat can be used are well known in the art of dye chemistry asevidenced, for example, by the teachings of Chem. Berichte 96, 1963, pp1551-1561, and Journal of Heterocyclic Chemistry, Oct. 1975, pp 883-887.

The couplers of Formula IV are prepared by methods, or methods analogousto those described in the literature, e.g., see also U.S. Ser. No.661,215. The reaction by which the couplers are prepared is illustratedby the following equation: ##STR8##

In addition to the examples below, the preparation of the couplers usedfor preparing the novel compounds of the invention are also described inA. Chem. 2, 153 (1962); C.A., 58, 453 g; Ber., 95, 1128 (1962); Ber.,60, 1607 (1927); and J. Pharm. Soc. Japan, 57, 1050 (1937); C.A. 32,33,985.

The invention will be further illustrated by the following examplesalthough it will be understood that these examples are included merelyfor purposes of illustration and is not intended to limit the scope ofthe invention.

EXAMPLE 16,6-Dimethyl-8-Keto-2-Phenyl-5,6,7,8-Tetrahydroimidazo[2,1-b]Benzothiazole

A 0.08 m. quantity each of2-amino-5,5-dimethyl-7-keto-4,5,6,7-tetrahydrobenzothiazole andα-bromoacetophenone are mixed in 150 ml. of chloroform and heated atreflux for 4 hours. The slurry is filtered hot and the insolubleintermediate product is suspended in 600 ml. of water containing 25 g.of sodium acetate. This suspension is heated slowly to boil over 21/2hours, then allowed to cool. The product is filtered off, washed wellwith water and dried yielding 12.5 g. of product melting at 175°-178° C.and having the structure: ##STR9##

EXAMPLE 2 2-Phenylimidazo[1,2-a]Pyrimidine

An equimolar mixture of 2-aminopyrimidine and α-bromoacetophenone areheated in absolute ethanol for several hours at 60°-70° C. Anhydrousether is added to precipitate the hydrobromide of the product. The freebase, melting at 202° C., is obtained by the action of aqueous Na₂ CO₃solution and has the formula ##STR10##

EXAMPLE 3 7-Methyl-2-Phenylimidazo[1,2-c]Pyrimidine

Substitution of 4-amino-6-methylpyrimidine in Example 2 yields a couplerwhich melts at 244° C. and has the structure: ##STR11##

EXAMPLE 4 2-Phenylimidazo[2,1-b]Benzothiazole

A 0.2 m. quantity each of 2-aminobenzothiazole and α-bromoacetophenoneare mixed in 350 ml. of chloroform and heated at reflux for 11/2 hours.After cooling, the solid intermediate product is filtered off andslurried in 2 l. of water containing 10 ml. of 48% hydrobromic acid.This is then heated to a boil, filtered hot, and after allowing to coolthe filtrate is basified with NH₄ OH to yield 6.8 g. of2-phenylimidazo[2,1-b]benzothiazole melting at 108°-10° C. and havingthe formula: ##STR12##

EXAMPLE 5 2-Phenylimidazo[1,2-a]Pyridine

0.1 m. Quantities of 2-aminopyridine and α-bromoacetophenone are heatedin 150 ml. of chloroform at reflux for 2 hours. The chloroform isevaporated and the oily residue taken up in 10% HCl, warmed, charcoaladded and filtered. The filtrate is neutralized with NH₄ OH and thesolid product isolated and recrystallized from ethanol. The yield ofproduct is 12.7 g., melts at 135°-137° C. and has the structure:##STR13##

EXAMPLE 6 2-Phenyl-5,6,7,8-Tetrahydroimidazo[2,1-b]Benzothiazole

0.1 m. Quantities of 2-amino-4,5,6,7-tetrahydrobenzothiazole andα-bromoacetophenone in 100 ml. of chloroform are heated at reflux for 2hours. After cooling, the solid is filtered off and slurred in 1 l. ofwater containing 40 g. of ammonium acetate. This suspension is heated toboiling over a 2-hour period and allowed to cool. The product iscollected, washed with water and dried. The yield of product is 19.8 g.melting at 158°-160° C. and having the formula: ##STR14##

EXAMPLE 7 6-Phenylimidazo[2,1-b]-1,3,4-Thiadiazole

10.1 g. of 2-amino-1,3,4-thiadiazole are dissolved in 160 ml. ofethanol, 19.9 g. of α-bromoacetophenone is added and the solution isheated and stirred at reflux for 1 hour. After cooling, the solid isfiltered off and dissolved in 750 ml. of water and 40 ml. of 48%hydrobromic acid. This solution is heated at reflux for 1 hour,neutralized by addition of solid ammonium acetate and refluxed 1/2 hourlonger. After cooling, the product is collected on a filter, washed withwater and dried. The yield of product is 13 g. melting at 127°-130° C.It has the formula: ##STR15##

EXAMPLE 8 6-Phenylimidazo[2,1-b]thiazole

Bromine (21.5 ml.) is added to a solution of 50 g. of acetophenone and0.1 g. of anhydrous AlCl₃ in 200 ml. of chlorobenzene. The additionrequires about 20 minutes and the temperature of the reaction solutionrises to about 35° C. Dry air is bubbled through the solution until allthe gaseous HBr is removed. 2-Aminothiazole (24 g.) is added and thereaction mixture stirred and heated on a steam bath for 1 hour. Thethick reaction mixture is filtered while still hot and the filter cakewashed with hexane. The dry product is slurried in 200 ml. of methanoland then diluted with a solution of 80 g. ammonium acetate in 1600 ml.of water. This suspension is stirred and heated to 80° C., then filteredand the product thus obtained is washed with 4 l. of water. The yield is70 g. of product which melts at 143°-144° C. and has the structure:##STR16##

Additional couplers can be prepared by employing techniques eitherpublished in the literature or analogous to those described in thepreceding examples.

The dyes of this invention can be applied to synthetic polyamide,polyester and cellulose acetate fibers according to known dispersedyeing techniques. Various dispersing and wetting agents can be employedin the dispersion of the finely divided dye compound in an essentiallyaqueous dyebath. Procedures by which the present dyes can be applied topolyamide textile materials are described, for example, in U.S. Pat.Nos. 3,100,134 and 3,320,021. Typically, the azo compound (16.7 mg.) isdispersed in 10 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a3% sodium lignin sulfonate solution is added, with stirring, and thevolume of the bath brought to 150 cc. with water. A 5 g. textile fabricmade of nylon 66 fibers is placed in the bath and worked 10 minuteswithout heat. The bath is then slowly brought to the boil over a30-minute period and then dyeing is carried out at the boil for onehour. The dyed fabric is then removed from the dyebath, rinsed withwater and dried in an oven at 250° F. Fabric samples thus dyed with thepresent dyes exhibit one or more of the improved properties set forthabove when tested in accordance with the procedures described, forexample, in the Technical Manual of the American Association of TextileChemists and Colorists, 1968 edition.

A typical general procedure by which polyester, e.g., poly(ethyleneterephthalate) can be dyed with the present dyes is as follows. The dyecake is dispersed by heating and agitating a dyepot containing the dyecake and methyl cellosolve. When the dyecake has been ground free oflumps and dissolved as much as possible in the methyl cellosolve, 2%based on weight of the fabric of Igepon T-51 and 2.0% based on weight ofthe fabric of sodium lignin sulfonate from a premixed solution of thetwo components is added. Sufficient demineralized water is added to makeabout a 30:1 bath ratio of water to dye and a small amount of Versene100 (sodium salt of ethylenediaminetetracetic acid) and Tanalon JDM-72(dye carrier) are added. The pH of the dyebath is adjusted to about 5.0with acetic acid. The fabric samples (wet-out) are entered into thedyepot and the entire contents thereof entered into a pressure dyeingcontainer. The container is sealed and entered into a High TemperatureLaunder-Ometer which is heated to 120° F. and rotation thereof started.The temperature of the Launder-Ometer is raised to 265° F. at the rateof about 5° F. per minute, and maintained at this temperature for 1hour. The Launder-Ometer is then cooled, and the fabric samples removedand scoured in demineralized water containing 1 g/l of neutral soap and1 g/l sodium carbonate. The samples are rinsed in cold demineralizedwater and dried at 250° F. in a forced air oven.

The following table shows exemplary dyes of the present invention.

                                      TABLE 1                                     __________________________________________________________________________     ##STR17##                                                                    Example                                                                            R.sup.1                                                                             R.sup.2 Ar         Z                                               __________________________________________________________________________    1    H     H       C.sub.6 H.sub.5                                                                           ##STR18##                                      2    H     H       C.sub.6 H.sub.5                                                                          "                                               3    CH.sub.3                                                                            CHO     C.sub.6 H.sub.5                                                                          "                                               4    CH.sub.3                                                                             ##STR19##                                                                            C.sub.6 H.sub.5                                                                          "                                               5    CH.sub.3                                                                            Cl      C.sub.6 H.sub.5                                                                          "                                               6    CH.sub.3                                                                            CN      C.sub.6 H.sub.5                                                                          "                                               7    CH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5                                                                          "                                               8    CH.sub.3                                                                            CONHC.sub.2 H.sub.4 OH                                                                C.sub.6 H.sub.5                                                                           ##STR20##                                      9    COOCH.sub.3                                                                         Br      C.sub.6 H.sub.5                                                                           ##STR21##                                      10   Br    H       C.sub.6 H.sub.5                                                                          "                                               11   CH.sub.3                                                                            Br      C.sub.6 H.sub.5                                                                           ##STR22##                                      12   CH.sub.3                                                                            Cl      C.sub.6 H.sub.5                                                                           ##STR23##                                      13   CH.sub.3                                                                            Br      C.sub.6 H.sub.5                                                                           ##STR24##                                      14   COCH.sub.3                                                                          Br      C.sub.6 H.sub.5                                                                           ##STR25##                                      15   CH.sub.3                                                                            Br      4-BrC.sub.6 H.sub.5                                                                       ##STR26##                                      16   CH.sub.3                                                                            Br      4,5-di(OH)C.sub.6 H.sub.3                                                                "                                               17   CH.sub.3                                                                            Br      4-dimethylamino-C.sub.6 H.sub.4                                                          "                                               18   CH.sub.3                                                                            Br      C.sub.6 H.sub.5                                                                          "                                               19   CH.sub.3                                                                            Br      C.sub.6 H.sub.5                                                                          "                                               20   Cl    H       C.sub.6 H.sub.5                                                                          "                                               21   CH.sub.3                                                                            COC.sub.2 H.sub.5                                                                     C.sub.6 H.sub.5                                                                          "                                               22   CH.sub.3                                                                            COC.sub.2 H.sub.5                                                                     C.sub.6 H.sub.5                                                                           ##STR27##                                      23   CH.sub.3                                                                            CN      C.sub.6 H.sub.5                                                                           ##STR28##                                      24   CH.sub.3                                                                            CN      C.sub.6 H.sub.5                                                                          "                                               25   CH.sub.3                                                                            CONH.sub.2                                                                            4-BrC.sub.6 H.sub.4                                                                       ##STR29##                                      26   CH.sub.3                                                                            CN      C.sub.6 H.sub.5                                                                           ##STR30##                                      27   CH.sub.3                                                                            SO.sub.2 C.sub.2 H.sub.5                                                              C.sub.6 H.sub.5                                                                          "                                               28   CH.sub.3                                                                            SCN     C.sub.6 H.sub.5                                                                          "                                               29   CH.sub.3                                                                            SCN     4-NO.sub.2C.sub.6 H.sub.4                                                                "                                               30   CHO   SCN     4-NO.sub.2C.sub.6 H.sub.4                                                                "                                               31   CH.sub.3                                                                            SO.sub.2 CH.sub.3                                                                     C.sub.6 H.sub.5                                                                           ##STR31##                                      32   C.sub.2 H.sub.5                                                                     CN      C.sub.6 H.sub.5                                                                           ##STR32##                                      33   C.sub.2 H.sub.5                                                                     CN      4-OCH.sub.3C.sub.6 H.sub.4                                                               "                                               34   H     H       C.sub.6 H.sub.5                                                                           ##STR33##                                      35   H     H       C.sub.6 H.sub.5                                                                           ##STR34##                                      36   CH.sub.3                                                                            CHO     C.sub.6 H.sub.5                                                                           ##STR35##                                      37   CH.sub.3                                                                            Cl      C.sub.6 H.sub.5                                                                           ##STR36##                                      38   CH.sub.3                                                                            CONHC.sub.2 H.sub.4 OH                                                                C.sub.6 H.sub.5                                                                           ##STR37##                                      39   Br    H       C.sub.6 H.sub.5                                                                           ##STR38##                                      40   H     H       C.sub.6 H.sub.5                                                                           ##STR39##                                      41   H     H       C.sub.6 H.sub.5                                                                           ##STR40##                                      __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR41##                                                                    Example   R.sup.1 R.sup.2      R.sup.3                                                                             R.sup.4                                  ______________________________________                                        1         H       H            H     H                                        2         CH.sub.3                                                                              Br           CH.sub.3                                                                            CH.sub.3                                 3         CH.sub.3                                                                              CHO          C.sub.6 H.sub.5                                                                     H                                        4         CH.sub.3                                                                              CONH.sub.2   CH.sub.3                                                                            CH.sub.2 C.sub.6 H.sub.5                 5         CH.sub.3                                                                              Cl           C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                          6         CH.sub.3                                                                              CN           H     H                                        7         CH.sub.3                                                                              COOC.sub.2 H.sub.5                                                                         CH.sub.3                                                                            CH.sub.3                                 8         CH.sub.3                                                                              CONHC.sub.2 H.sub.4 OH                                                                     C.sub.6 H.sub.5                                                                     H                                        9         CH.sub.3                                                                              Br           CH.sub.3                                                                            CH.sub.2 C.sub.6 H.sub.5                 10        C.sub.2 H.sub.5                                                                       Br           C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                          11        CH.sub. 3                                                                             Cl           H     H                                        12        CH.sub.3                                                                              SCN          CH.sub.3                                                                            CH.sub.3                                 13        CH.sub.3                                                                              COCH.sub.3   C.sub.6 H.sub.5                                                                     H                                        14        CH.sub.3                                                                              COC.sub.2 H.sub.5                                                                          CH.sub.3                                                                            CH.sub.2 C.sub.6 H.sub.5                 15        CH.sub.3                                                                              Br           C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                          16        CH.sub.3                                                                              SO.sub.2 CH.sub.3                                                                          H     H                                        17        CH.sub.3                                                                              CN           CH.sub.3                                                                            CH.sub.3                                 18        CH.sub.3                                                                              CN           C.sub.6 H.sub.5                                                                     CH.sub.3                                 19        CH.sub.3                                                                              Br           C.sub.6 H.sub.5                                                                     H                                        ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A compound having the formula ##STR42## wherein R¹ and R²are each selected from cyano, bromo, hydrogen, chloro, formyl, loweralkoxycarbonyl, lower alkyl, lower alkylsulfonyl, thiocyano, carbamoyl,lower alkylcarbamoyl, and lower alkanoyl; Z represents the atomsnecessary to complete a fixe or six membered ring which is unsubstitutedor substituted with nitrogen, oxygen, sulfur or a combination thereof;and Ar is a benzene ring which is unsubstituted or substituted with upto three of lower alkyl, lower alkoxy, halogen, hydroxy, loweralkylamino, nitro or cyano.
 2. A compound according to claim 1 wherein Zis selected from ##STR43## wherein R⁵ represents a group selected fromhydrogen, lower alkyl, lower alkoxy and halogen.
 3. A compound accordingto claim 1 having the formula ##STR44##
 4. A compound according to claim1 having the formula ##STR45##